Method for preparing modified PBAT through step-by-step regulation and control
Through the step-by-step method of controlling the modified PBAT, the problem of difficult control of the reaction ratio in the prior art is solved, and the fine control of the PBAT segment structure is achieved, and the tensile strength and toughness of the material are improved.
Patent Information
- Application Number
- CN202411736997.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-29
- Publication Date
- 2025-02-11
AI Technical Summary
In the existing PBAT synthesis, the ratio of terephthalic acid, adipic acid and 1,4-butanediol during the reaction process is difficult to control, resulting in a deviation between the segment structure and the design value, especially when the material performance is improved and modified, it is difficult to Controls the structure of molecular segments.
The method of controlling modified PBAT in step by step is used to gradually control the reaction ratio of terephthalic acid, adipic acid and 1,4-butylene glycol through step-by-step reaction, and tetrabutyl titanate and triphenyl phosphate are used as The catalyst is subjected to vacuum and nitrogen replacement treatment to ensure strict control of reaction conditions.
Through step-by-step synthesis method, the segment structure of PBAT can be finely controlled, the tensile strength and toughness of the material can be improved, and the need for improving material performance and modification.
Smart Images
Figure CN119409956A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of biodegradable materials, and in particular to a method for preparing modified PBAT by step-by-step regulation. Background Art
[0002] Polybutylene adipate / terephthalate (PBAT) is a new type of thermoplastic aliphatic-aromatic copolyester biodegradable plastic. Due to its good ductility, elongation at break, heat resistance and impact resistance, it is widely used in plastic packaging, agricultural mulch, sanitary products and biomedicine. Based on the current situation of my country's rich coal, poor oil and little gas resources, efficient use of coal chemical downstream products to produce terephthalic acid (TPA), adipic acid (AA) and 1,4-butanediol (BDO), the raw materials for synthesizing biodegradable polyester PBAT, reduces dependence on petroleum resources and provides an important way for the high-quality utilization of coal chemical downstream products.
[0003] In the current reports on PBAT synthesis, for the sake of simplicity, many one-pot copolymerization reactions are used to generate PBAT polymers. However, during the one-pot reaction, the ratio of terephthalic acid, adipic acid and 1,4-butanediol is difficult to control, and the segment structure will deviate from the designed value. Especially when the material is modified to improve its performance, it is more inconvenient to control the structure of the molecular segment. Based on this, the present invention designs a step-by-step control method for preparing modified PBAT. Summary of the invention
[0004] The purpose of the present invention is to solve the problems in the prior art and to propose a method for preparing modified PBAT by step-by-step regulation.
[0005] A method for preparing modified PBAT by step-by-step regulation comprises the following steps:
[0006] Weigh terephthalic acid and 1,4-butanediol in a molar ratio (1:1 to 1:2.5), put them into reaction container a, add appropriate amounts of catalysts tetrabutyl titanate and triphenyl phosphate and stir evenly for 0 to 24 hours. Reaction container a is evacuated, filled with nitrogen or argon, and the inert gas is replaced 3 times, and then continuously evacuated to maintain the vacuum pressure at -0.02 to -0.06MPa. Reaction container a is heated and heated to 150 to 180°C in the first stage reaction, stirred for 1 to 2 hours, and the second stage reaction continues to heat to 220 to 250°C, stirred for 1 to 10 hours to obtain prepolymer A. Among them, tetrabutyl titanate is 0.1‰ to 10‰ of the total mass of terephthalic acid and 1,4-butanediol. Among them, triphenyl phosphate is 0.1‰ to 10‰ of the total mass of terephthalic acid and 1,4-butanediol.
[0007] Weigh adipic acid and 1,4-butanediol in a molar ratio (1:1-1:2), put them into the reaction vessel b, add appropriate amounts of catalysts tetrabutyl titanate and triphenyl phosphate and stir evenly for 0-24 hours. The reaction vessel b is evacuated, filled with nitrogen or argon, and the inert gas is replaced 3 times, and then continuously evacuated to maintain the vacuum pressure at -0.02-0.06MPa. The reaction vessel b is heated and heated to 150-180°C in the first stage reaction, stirred for 1-2 hours, and the second stage reaction continues to heat to 210-230°C, stirred for 1-10 hours to obtain prepolymer B. Among them, tetrabutyl titanate is 0.1‰-10‰ of the total mass of the adipic acid and 1,4-butanediol. Among them, triphenyl phosphate is 0.1‰-10‰ of the total mass of the terephthalic acid and 1,4-butanediol.
[0008] Weigh lactic acid and isosorbide in a molar ratio (1:1-2:1), put them into reaction vessel c, add an appropriate amount of catalyst zinc acetate and stir evenly for 0-24 hours. Reaction vessel c is evacuated, filled with nitrogen or argon, and replaced with inert gas 3 times, and then continuously evacuated to maintain the vacuum pressure at -0.02-0.06MPa. Reaction vessel c is heated and heated to 100-120°C in the first stage reaction, stirred for 1-2 hours, and continued to heat to 145-165°C in the second stage reaction, stirred for 1-10 hours to obtain prepolymer C. Wherein zinc acetate is 1‰-5‰ of the total mass of lactic acid and isosorbide.
[0009] Tetrabutyl titanate, zinc acetate, sodium bicarbonate, phosphoric acid and ethyl orthosilicate were added to anhydrous ethanol for full hydrolysis, cooled and filtered to obtain catalyst D.
[0010] Add prepolymers A, B, and C into the reaction vessel d, add the prepared catalyst D, replace the inert gas 3 times, and then continue to evacuate to keep the vacuum pressure below 50 Pa. Heat to 210-260°C and stir for 4-10 hours, cool and output, and a new type of biodegradable material can be obtained.
[0011] Compared with the existing technology, the advantages of the present invention are: the present invention starts from improving the material performance, performs step-by-step synthesis, the material segment structure is controllably adjustable, and the obtained material has the characteristics of high tensile strength and good toughness. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Figure 1 The present invention provides a process diagram for a step-by-step method for preparing modified PBAT.
[0013] Figure 2 This is a DSC test diagram of a sample of preferred embodiment 3 in the method for preparing modified PBAT by step-by-step regulation proposed by the present invention.
[0014] Figure 3 This is a sample TG test diagram of preferred embodiment 3 in the method for preparing modified PBAT by step-by-step regulation proposed by the present invention. DETAILED DESCRIPTION
[0015] Example 1
[0016] Weigh 200g of terephthalic acid and 216g of 1,4-butanediol, put them into reaction container a, add 0.42g of tetrabutyl titanate and 0.21g of triphenyl phosphate and stir evenly. After 0.5h, vacuumize the reaction container a, fill it with nitrogen or argon, replace the inert gas 3 times, and then continue to vacuumize, keeping the vacuum pressure at -0.04MPa. Heat the reaction container a, heat it to 180℃ in the first stage reaction, stir it for 2 hours, and continue to heat it to 230℃ in the second stage reaction, stir it for 4 hours to obtain prepolymer A.
[0017] Weigh 117g of adipic acid and 144g of 1,4-butanediol, put them into reaction container b, add 0.26g of tetrabutyl titanate and 0.13g of triphenyl phosphate and stir evenly for 0.5h. Vacuum reaction container b, fill with nitrogen or argon, replace inert gas 3 times, and then continue to evacuate, keeping the vacuum pressure at -0.05MPa. Heat reaction container b, heat to 170℃ in the first stage reaction, stir for 2 hours, continue to heat to 220℃ in the second stage reaction, stir for 3 hours, and obtain prepolymer B.
[0018] Weigh 54g of lactic acid and 29g of isosorbide, put them into reaction vessel c, add 0.17g of zinc acetate and stir evenly for 0.5h. Vacuum reaction vessel c, fill with nitrogen or argon, replace inert gas 3 times, and then continue to evacuate, keeping the vacuum pressure at -0.05MPa. Heat reaction vessel c, heat to 120°C in the first stage reaction, stir for 1 hour, continue to heat to 150°C in the second stage reaction, stir for 3 hours, and obtain prepolymer C.
[0019] 0.5 g of tetrabutyl titanate, 0.2 g of zinc acetate, 0.1 g of sodium bicarbonate, 0.1 g of phosphoric acid and 0.2 g of ethyl orthosilicate were added to anhydrous ethanol for sufficient hydrolysis, cooled and filtered to obtain catalyst D.
[0020] Add prepolymers A, B, and C into reaction vessel d, add the prepared catalyst D, replace the inert gas 3 times, and then continue to evacuate to keep the vacuum pressure below 50 Pa. Heat to 220°C and stir for 6 hours, cool and output, and you can get biodegradable material 1#.
[0021] Example 2
[0022] Prepolymer A was prepared in the same manner as in Example 1.
[0023] Weigh 88g of adipic acid and 81g of 1,4-butanediol, put them into reaction container b, add 0.17g of tetrabutyl titanate and 0.09g of triphenyl phosphate and stir evenly for 0.5h. Vacuum reaction container b, fill with nitrogen or argon, replace inert gas 3 times, and then continue to evacuate, keeping the vacuum pressure at -0.05MPa. Heat reaction container b, heat to 170°C in the first stage reaction, stir for 2 hours, continue to heat to 220°C in the second stage reaction, stir for 3 hours, and obtain prepolymer B.
[0024] Weigh 72g of lactic acid and 29g of isosorbide, put them into reaction vessel c, add 0.2g of zinc acetate and stir evenly for 0.5h. Vacuum reaction vessel c, fill with nitrogen or argon, replace inert gas 3 times, and then continue to evacuate, keeping the vacuum pressure at -0.05MPa. Heat reaction vessel c, heat to 120°C in the first stage reaction, stir for 1 hour, continue to heat to 150°C in the second stage reaction, stir for 3 hours, and obtain prepolymer C.
[0025] Catalyst D was prepared in the same manner as in Example 1.
[0026] Add prepolymers A, B, and C into reaction vessel d, add the prepared catalyst D, replace the inert gas 3 times, and then continue to evacuate to keep the vacuum pressure below 50 Pa. Heat to 220°C and stir for 6 hours, cool and output, and you can get biodegradable material 2#.
[0027] Example 3
[0028] Prepolymer A was prepared in the same manner as in Example 1.
[0029] Prepolymer B was prepared in the same manner as in Example 1.
[0030] Weigh 72g of lactic acid and 58g of isosorbide, put them into reaction vessel c, add 0.26g of zinc acetate and stir evenly for 0.5h. Vacuum reaction vessel c, fill with nitrogen or argon, replace inert gas 3 times, and then continue to evacuate, keeping the vacuum pressure at -0.05MPa. Heat reaction vessel c, heat to 120°C in the first stage reaction, stir for 1 hour, continue to heat to 160°C in the second stage reaction, stir for 3 hours, and obtain prepolymer C.
[0031] Catalyst D was prepared in the same manner as in Example 1.
[0032] Add prepolymers A, B, and C into reaction vessel d, add the prepared catalyst D, replace the inert gas 3 times, and then continue to evacuate to keep the vacuum pressure below 50 Pa. Heat to 230°C and stir for 6 hours, cool and output, and you can get biodegradable material 3#.
[0033] Example 4
[0034] Weigh 200g of terephthalic acid and 162g of 1,4-butanediol, put them into reaction container a, add 0.36g of tetrabutyl titanate and 0.18g of triphenyl phosphate and stir evenly for 0.5h. Vacuum reaction container a, fill with nitrogen or argon, replace inert gas 3 times, and then continue to evacuate, keeping the vacuum pressure at -0.04MPa. Heat reaction container a, heat to 180℃ in the first stage reaction, stir for 2 hours, continue to heat to 230℃ in the second stage reaction, stir for 4 hours, and obtain prepolymer A.
[0035] Weigh 117g of adipic acid and 108g of 1,4-butanediol, put them into reaction container b, add 0.22g of tetrabutyl titanate and 0.11g of triphenyl phosphate and stir evenly for 0.5h. Vacuum reaction container b, fill with nitrogen or argon, replace inert gas 3 times, and then continue to evacuate, keeping the vacuum pressure at -0.05MPa. Heat reaction container b, heat to 170°C in the first stage reaction, stir for 2 hours, continue to heat to 220°C in the second stage reaction, stir for 3 hours, and obtain prepolymer B.
[0036] Weigh 36g of lactic acid and 58g of isosorbide, put them into reaction vessel c, add 0.19g of zinc acetate and stir evenly for 0.5h. Vacuum reaction vessel c, fill with nitrogen or argon, replace inert gas 3 times, and then continue to evacuate, keeping the vacuum pressure at -0.05MPa. Heat reaction vessel c, heat to 120°C in the first stage reaction, stir for 1 hour, continue to heat to 160°C in the second stage reaction, stir for 3 hours, and obtain prepolymer C.
[0037] Catalyst D was prepared in the same manner as in Example 1.
[0038] Add prepolymers A, B, and C into reaction vessel d, add the prepared catalyst D, replace the inert gas 3 times, and then continue to evacuate to keep the vacuum pressure below 50 Pa. Heat to 230°C and stir for 6 hours, cool and output, and you can get biodegradable material 4#.
[0039] Example 5
[0040] Prepolymer A was prepared in the same manner as in Example 4.
[0041] Prepolymer B was prepared in the same manner as in Example 4.
[0042] Prepolymer C was prepared in the same manner as in Example 4.
[0043] 0.5 g of tetrabutyl titanate, 0.1 g of zinc acetate, 0.1 g of sodium bicarbonate, 0.05 g of phosphoric acid and 0.1 g of ethyl orthosilicate were added to anhydrous ethanol for sufficient hydrolysis, cooled and filtered to obtain catalyst D.
[0044] Add prepolymers A, B, and C into reaction vessel d, add the prepared catalyst D, replace the inert gas 3 times, and then continue to evacuate to keep the vacuum pressure below 50 Pa. Heat to 230°C and stir for 10 hours, cool and output, and you can get biodegradable material 5#.
[0045]
[0046] It is known from common technical knowledge that the present invention can be implemented by other embodiments that do not deviate from its spirit or essential features. Therefore, the above disclosed embodiments are only illustrative in all respects and are not exclusive. All changes within the scope of the present invention or within the scope equivalent to the present invention are included in the present invention.
Claims
1. A method for preparing modified PBAT by step-by-step control, characterized in that: The following steps are involved: S1. Weigh terephthalic acid and 1,4-butanediol in molar ratio, put them into reaction container a, add catalyst tetrabutyl titanate and triphenyl phosphate and stir evenly for 0 to 24 hours, then evacuate the reaction container a, fill it with nitrogen or argon, and replace the inert gas 3 times, then continue to evacuate, heat the reaction container a, and increase the temperature in stages to obtain prepolymer A. S2. Weigh adipic acid and 1,4-butanediol in molar ratio, put them into reaction container b, add catalysts tetrabutyl titanate and triphenyl phosphate and stir evenly for 0 to 24 hours, evacuate reaction container b, fill with nitrogen or argon, replace inert gas 3 times, and then continue to evacuate, heat reaction container b to obtain prepolymer B. S3. Weigh lactic acid and isosorbide in molar ratio, put them into reaction container c, add zinc acetate catalyst and stir evenly for 0 to 24 hours, evacuate reaction container c, fill it with nitrogen or argon, replace the inert gas 3 times, and then continue to evacuate, heat reaction container c to obtain prepolymer C. S4. Tetrabutyl titanate, zinc acetate, sodium bicarbonate, phosphoric acid and ethyl orthosilicate are added to anhydrous ethanol for sufficient hydrolysis, cooled and filtered to obtain catalyst D. S5. Add prepolymers A, B, and C into reaction container d, add the prepared catalyst D, replace the inert gas 3 times, and then continue to evacuate, keep the vacuum pressure below 50 Pa, heat and stir, cool and output, and complete the material processing.
2. The method for preparing modified PBAT by step-by-step control according to claim 1, characterized in that: In step S1, the molar ratio of terephthalic acid to 1,4-butanediol is 1:1 to 1:2.5, tetrabutyl titanate is 0.1‰ to 10‰ of the total mass of terephthalic acid and 1,4-butanediol, and triphenyl phosphate is 0.1‰ to 10‰ of the total mass of terephthalic acid and 1,4-butanediol.
3. The method for preparing modified PBAT by step-by-step control according to claim 1, characterized in that: In step S2, the molar ratio of adipic acid and 1,4-butanediol is 1:1-1:2, tetrabutyl titanate is 0.1‰-10‰ of the total mass of the adipic acid and 1,4-butanediol, and triphenyl phosphate is 0.1‰-10‰ of the total mass of the terephthalic acid and 1,4-butanediol.
4. The method for preparing modified PBAT by step-by-step control according to claim 1, characterized in that: In step S3, the molar ratio of lactic acid to isosorbide is 1:1 to 2:1, and the amount of zinc acetate is 1‰ to 5‰ of the total mass of the lactic acid and isosorbide.
5. The method for preparing modified PBAT by step-by-step control according to claim 1, characterized in that: During the vacuuming operation, the vacuum pressure is maintained at -0.02 to -0.06 MPa.
6. The method for preparing modified PBAT by step-by-step control according to claim 1, characterized in that: The zinc acetate is 1‰ to 5‰ of the total mass of the lactic acid and isosorbide.
7. The method for preparing modified PBAT by step-by-step control according to claim 1, characterized in that: In step S1, the heating of the reaction container a is divided into two stages. In the first stage, the reaction temperature is raised to 150-180°C and stirred for 1-2 hours. In the second stage, the reaction temperature is further raised to 220-250°C and stirred for 1-10 hours.
8. The method for preparing modified PBAT by step-by-step control according to claim 1, characterized in that: In step S2, the heating of the reaction container b is divided into two stages. In the first stage, the reaction temperature is raised to 150-180°C and stirred for 1-2 hours. In the second stage, the reaction temperature is further raised to 210-230°C and stirred for 1-10 hours.
9. The method for preparing modified PBAT by step-by-step control according to claim 1, characterized in that: In step S3, in step S, the heating temperature of the reaction container c is divided into two stages. In the first stage, the reaction temperature is raised to 100-120°C and stirred for 1-2 hours. In the second stage, the reaction temperature is further raised to 145-165°C and stirred for 1-10 hours.
10. The method for preparing modified PBAT by step-by-step control according to claim 1, characterized in that: In step S3, 72 g of lactic acid and 58 g of isosorbide are weighed and put into reaction vessel c, 0.26 g of zinc acetate is added and stirred evenly for 0.5 h, the reaction vessel c is evacuated, the inert gas is replaced 3 times, and then the evacuation is continued, and the vacuum pressure is maintained at -0.05 MPa. The reaction vessel c is heated and the temperature is increased to 120° C. in the first stage reaction, and stirred for 1 hour. The temperature is continued to be increased to 160° C. in the second stage reaction, and stirred for 3 hours to obtain prepolymer C. In step S5, the temperature is increased to 230° C. and stirred for 6 hours, and the product is cooled and output.